TiB2 and copper are difficult to be sintered together by conventional sintering process. In this article, the TiB2/Cu functionally graded materials (FGMs) were successfully fabricated via spark plasma sintering (SPS) method, in which a temperature gradient was achieved by using a specially designed mold and a two-step sintering was performed. The SEM observations show that the TiB2/Cu FGMs have dense microstructures. The XRD analysis suggests that no new phases were introduced into the TiB2/Cu composites after mechanical milling or SPS process. The TiB2/(TiB2+Cu)/Cu FGMs are promising electrode materials of solar thermoelectric modules.